US2855365A - Drilling fluid - Google Patents

Description

United States Patent DRILLING FLUID No Drawing. Application October 25, 1955 Serial No. 542,780

9 Claims. (Cl. 2528.5)

This invention relates to novel polymeric compositions and, more particularly, to hydrolyzed polymers of hydrocyanic acid. The invention also relates to the use of such hydrolyzed polymers of hydrocyanic acid as dispersing or deflocculating agents in aqueous dispersions or suspensions of finely divided solid materials such as pigments, clays, and the like.

It has been known for some time that hydrocyanic acid will polymerize to yield various types of polymeric products, depending upon the particular conditions employed. In the earliest art it had frequently been observed that upon standing, especially when exposed to the action of light, an aqueous solution of hydrocyanic acid yielded a brown precipitate generally referred to as azulmic compounds or sometimes termed azulmic acid. U. S. Patent 1,464,802, issued to Bohart August 14, 1923, describes the production of a brownish-black amorphous precipitate from aqueous solutions of hydrocyanic acid. Another method for the preparation of hydrocyanic acid polymers has been disclosed by Adams et al. in U. S. Patent 2,069,543, who also claim a soft, dull black, apparently amorphous polymerized product of hydrocyanic acid. While these polymers have been recognized and prepared, they have found such limited utility that they have achieved little commercial significance. The earliest products were, of course, no more than chemical curiosities. The polymer made by Bohart was an insoluble material which he treated to make soluble for use as a dye stufi in producing various shades of yellow and brown. Adams et al. describe their products as being particularly useful as activators in chemical reactions, particularly as activators in the metal-treating industry. This is the extent to which polymers of hydrocyanic acid have up to now been demonstrated to be useful.

It has now been discovered that significantly improved aqueous dispersions of finely divided solid materials can be prepared by incorporating therein a minor amount of novel hydrolyzed polymers of hydrocyanic acid preferably in the form of their salts. These hydrolyzed HCN polymers have proved to be particularly useful in the preparation of aqueous dispersions of pigments and in the preparation of aqueous dispersions of clays to be used as drilling muds.

It is an object of this invention, therefore, to provide a new class of polymers of hydrocyanic acid.

It is also an object of the invention to provide a new class of polymers of hydrocyanic acid characterized by a high degree of surface activity and to provide as well a process by which such polymers can be produced on a commercial scale.

It is another object of this invention to provide improved aqueous dispersions of finely divided solid materials.

It is still another object of the invention to provide novel compositions of matter comprising hydrofyzed polymers of hydrocyanic acid incorporated in aqueous dispersions or suspensions of finely divided solid materials such as clays, pigments, soot, and the like.

ice

It is a specific object of this invention to provide improved aqueous dispersions of finely divided pigments.

Another specific object of this invention is to provide proved aqueous dispersions or suspensions of clays having particular utility in drilling muds.

It is still another object of this invention to provide a method of controlling the viscosity of aqueous drilling muds without adversely afiecting other properties such as gel strength and filtration rate.

A still further object of the invention is to provide an aqueous drilling fluid having controlled viscosity.

Further objects and advantages will become apparent from the following description of the invention.

According to the invention, the novel hydrocyanic acid polymers are prepared by polymerizing liquid hydrocyanic acid in the presence of an alkaline catalyst and thereafter hydrolyzing and/ or saponifying the polymer by treatment with water in the presence of an acid or an alkali. In accordance with the invention also, the dispersion of a finely divided solid such as a pigment, clay, and the like suspended in an aqueous medium may be readily effected by incorporating in said suspension a small quantity of a hydrolyzed polymer of HCN. Consequently, in addition to the hydrolyzed HCN polymers per se, the invention is also considered as encompassingcompositions of matter which are mixtures comprising finely divided solid materials such as various clays, pigments, etc., suspended in an aqueous vehicle and a suflicient amount of a hydrolyzed polymer of HCN to maintain the viscosity of the mixture at the desired level.

While the structure of the polymer, (HCN),,, has not been definitely established, several possible structures have been postulated. Of these, the more likely, based upon the observed activity of the hydrolyzed materials, appears to be either NH FNH Eaaltl... it L J aifiliil LN 1.

Upon hydrolysis the polymer in (1) would then have the structure corresponding to wherein X may be hydrogen or a salt-forming cation preferably selected from the group consisting of the alkali metals and ammonium. Actually, the hydrolyzed polymer of the invention is probably a mixture in varying proportions of materials represented by the structures in (4) and (5) above with that represented by (5) predominating.

The following examples of a practical method of preparing the novel polymeric materials of the invention are presented to illustrate the invention, but arenot to be construed as limiting it in any manner.

3 EXAMPLE I Approximately 350 g. of liquid hydrocyanic acid (99+% HCN) and 3.5 g. of triethyl amine were charged to a 1-liter, three-necked, round-bottomed reaction fiask equipped with a stirrer, a thermometer and a condenser cooled by circulating cold water C.). The mixture was stirred for 72 hr. at 25 C. Excess hydrocyanic acid was then vented and the solid product was ground in a ball mill for 2 hours. The amount of polymer, a dark brown solid material, recovered was 252 g., representing a once-through yield based on HCN of 72%.

A SO-g. sample of the polymer was charged with 37.8 g; of sodium hydroxide (C. P.) and 150 ml. of water to a three-necked, two-liter flask fitted with a reflux condenser service with tap water at 25 C., a stirrer, and a thermometer. Quantities employed were based on the assumption that one-half of the nitrogen in the polymer was available for hydrolysis and hence approximately 0.925 mol of polymer and 0.923 mol of NaOH were present in the charge. This assumption actually had good basis intact. The results of experiments with polymer of known nitrogen content (as determined by analysis) which was hydrolyzed with varying quantities of caustic and then analyzed for sodium content and residual nitrogen content verified that the 50% figure is fairly accurate. Theoretical nitrogen content of the completely hydrolyzed material should be about 14% on this basis. The mixture was refluxed for ten hours at a temperature of approximately 100 C., during which time ammonia was evolved. It was then dried overnight at 135 C. and 760 mm. Hg and ground in a ball mill. The amount of hydrolyzed polymer recovered was 84.3 g. Based on the polymer charged and the assumed possible theoretical yield of 86.0 g., this represents a yield of 98%. Kjeldahl analysis of the hydrolyzed polymer showed a nitrogen content of 14.2%. The hydrolyzed polymer was soluble in water so a 10% aqueous solution was prepared for evaluation.

EXAMPLE II Into a 16-02. wide-mouthed jar was charged 210 g. of commercial liquid hydrocyanic acid (99+% HCN) and 2.1 g. of triethylamine. The jar was covered loosely with a lid and a one-liter beaker was inverted over it. The mixture was allowed to stand thus overnight (16l8 hr.) at room temperature (25 G). Since the polymerization reaction is an exothermic one, the temperature of the reaction mixture became somewhat elevated but no attempt was made to record the maximum temperature during the reaction. At the end of the reaction period all the unreacted HCN had volatilized and the dry polymer was removed and ground in a ball mill for two hours. The dark brown solid polymer recovered weighed 81 g., representing a once-throughmolal yield of 38.6% based on HCN.

Two pounds of the polymer were then prepared in this fashion and two samples of the polymeric material were hydrolyzed by the same procedure as given in Example The table below summarizes I to yield the sodium salt. these runs.

Hydro- N2 Polymer (g.) Water NaOH lyzed Content, Yield (1.111.) (g.) Polymer Percent 1 Percent of theoretical yield based on estimate that 50% of the nitrogen in the polymer is available for hydrolysis. 2 Percent of theoretical yield based on estimate that 25% of the nitrogen in the polymer is available for hydrolysis.

While specific reactants, quantities of reactants, and reaction conditions have been set forth in the preceding examples, the process for the preparation of the novel compounds of the invention is subject to substantial variations. For example, although the liquid hydrocyanic feed should preferably be of the highest order of purity and anhydrous, acid of concentrations down to where the major contaminant is water, may be employed.

Although triethyl amine is definitely the preferred catalyst, other aliphatic and aromatic amines, either primary, secondary or tertiary, which will dissolve in liquid HCN, may be employed. Particular ones which are suitable include, for example, methyl amine, trimethyl amine, ethyl amine, tri-n-butyl amine, n-propyl amine, aniline, toluidine, benbylamine, the naphthylamines, hydrazine, and the like. Other satisfactory catalysts include compounds which are alkaline in reaction when dissolved in liquid HCN such as the alkali metal hydroxides, potassium and sodium hydroxide, for example, sodium and potassium carbonates, and ammonium hydroxide or ammonia.

The amount of catalyst employed may also be varied within rather wide limits. Amounts ranging from as little as 0.1% up to 10% by weight of the HCN charge are satisfactory. However, with very small percentages of catalyst the time required for completion of the reaction is considerably extended. Preferred catalyst concentrations for reasonable or practical reaction times lie in the range from about 1 to about 5%. The rate of polymerization is linear with catalyst concentration. Usually, doubling the concentration of a given catalyst increases the yield for a given time period by a factor of approxi mately 2.5. However, it has been demonstrated that the concentration of catalyst employed has no significant eflect on the average molecular Weight of the hydrolyzed HCN polymer produced.

The polymerization reaction is a liquid-phase one which occurs readily at the boiling point of HCN at approximately atmospheric pressure and the application of external heat is not required. Best results are obtained ditions are too drastically different from those outlined above.

The rate of reaction and hence the reaction time is somewhat dependent upon the catalyst concentration. Generally, with the preferred quantity of 1 to 5% of catalyst by weight of the HCN charge, satisfactory yields are obtained in reaction periods of from about 8 to about 10 hours. Longer times up to 16 to 18 hours generally will give improved yields. The rate of polymerization at atmospheric pressure is linear with time and a two fold increase in reaction time will result in a yield increased by a factor of 2.5. In a practical process, therefore, a balance between yield and reaction time must be struck based on the economic considerations deemed important. Unreacted HCN can, of course, be recovered, as can the unused catalyst. It has. been found that the nature of the polymer is not affected to any particular extent by the time required for polymerization. Poly mers produced over a 70-hour reaction period that have been subsequently hydrolyzed have been found to have substantially the same molecular weight as those made in 17.5 hours under the same conditions of temperature, pressure, and catalyst concentration.

Upon completion of the reaction, the polymeric products formed are readily recovered by allowing excess HCN, if any is present, to evaporate and then subjecting the solid material to drying by external heating.

Conditions under which hydrolysis is'elfect ed may likewise be varied to some extent depending upon the product desired, i. e., whether'the desired form of the hydrolyzed polymer is the free acid or the salt. Hydrolysis is preferably carried out in the presence of a base such as the alkali metal hydroxides and ammonium hydroxide. However, acid hydrolysis may be employed in which case suitable acids are mineral acids such as sulfuric acid and hydrochloric acid.

' Generally, for complete hydrolysis of all the nitrogen which is available in the polymer for conversion to carboxyl groups, at least two molecular parts of water and one molecular part of base are employed per part of polymer. For practical purposes and in cases where as complete hydrolysis as possible is desired so that the nitrogen content of the hydrolyzed polymer is kept at a minimum, water is usually employed in excess. The extent of hydrolysis may, of course, also be controlled by regulating the amount of base employed. If less than complete hydrolysis is desired, then proportionately smaller quantities of base are employed.

The hydrolyzing reaction occurs to a minor extent at temperatures as low as 25 C. and thus the step maybe carried out at any temperature within the broad range from about 25 C. to about 200 C. Optimum results are achieved usually at temperatures in the range from about 100 C. to about 160 C. at atmospheric pressure or in suitable equipment at the higher temperatures under autogenous pressure. When operating within the preferred temperature range, a reaction time of about 6 to about 12 hours is satisfactory, while a time from about 9 to-10 hours is preferred. Extended periods of time in excess of those mentioned, other conditions being constant, result in little variation in residual nitrogen in the finished product.

The product resulting from hydrolysis is usually an aqueous solution which may be used as such or from which the solid hydrolyzed polymer may be recovered by evaporative drying, for example.

These novel hydrolyzed polymers of hydrocyanic acid have unusual characteristics or properties which make them of outstanding value as dispersing agents in the preparation of dispersions or suspensions of finely divided solid materials in an aqueous medium. In the manufacture of paints, for example, practically all pigments employed, particularly inorganic pigments, are prepared or processed in aqueous media and are initially recovered as a pulp or paste. In the preparation of aqueous pigment pulps themselves as well as in the dry grinding of pigments intended for water dispersions, surface active agents are often used to improve the degree of dispersion. The degree of dispersion of the pigment has a strong influence on the rheological properties of the paint as well as upon its covering power. Materials used in the prior art for dispersing pigments have been many and varied and have included, for example, naphthalene sulfonates, proteins, ligninsulfonates, fatty alkyl sulfates and quaternary ammonium compounds. It has now been determined that hydrolyzed polymers of HCN are particularly effective dispersing agents for pigments. The hydrolyzed polymers of HCN are characterized as products which ".by their presence act to prevent flocculation or agglomeration of solid particles of pigment suspended in water. In contrast to the compounds so employed in the prior art,

smaller amounts of the hydrolyzed polymer of HCN are required to promote a comparable degree of dispersion in pigments. With most dispersants, further addition after maximum thinning has been attained is characterized by an immediate increase in viscosity. This is not the case, however, with the thinners of the present invention since maximum thinning is maintained over a wider range of dispersant concentration and the likelihood of overtreatment is, therefore, minimized. The latter are also more desirable than those of the prior art for the reason that they maintain a constant low'level of viscosity over a much wider solids concentration range. They thus have the advantage of permitting the preparation of suspension of much higher solids concentration per given quantity of dispersing agent. I

The dispersing agents of the invention are effective generally with all pigments. Of the many in existence which can be dispersed in aqueous medium using the thinning agents described herein are ferric oxide, iron blues, red lead, white lead (basic carbonate), white lead (basic sulfate), lead chromate, zinc oxide, zinc chromate, zinc sulfide, lithopone, chromium oxide, titanium dioxide (Anatase), titanium dioxide (Rutile), antimony oxide,

cadmium sulfide, lead titanate, and the like. They are also useful with extended pigments such as titaniumbarium, titanium-calcium, and zinc sulfide-magnesium pigments or with any combinations of pigments used to provide pigments of other than the primary colors such as lead chromate-lead oxide for making lighter shades of chrome orange, and iron blue and lead chromate for making chrome greens.

The quantity of dispersing agent to be used depends, of course, on the degree of dispersion desired, or, in other words, the consistency or fluidity desired, the particle size of the dispersate, and the concentration of the dispersion. In general, from 0.05% to 5% by weight of the dispersing agents of the invention based on the dispersate will give good results. This applies to all types of dispersates, whether or not they be pigments. The hydrolyzed polymers of HCN may be added to the pigment suspension as an aqueous solution or as a solid in powdered form or it may be incorporated as a dry solid with the dry pigment in the grinding or milling operation. Alternatively, the dispersion and mixing may take place simultaneously by intimately mixing the pigment with water and the dispersing agent.

The effectiveness of the HCN polymers of the invention as dispersing agents for pigments is illustrated in the following examples. Viscosimetric measurements have been employed for evaluating dispersing action. The viscosity of the system is measured and the fluidity of the sample is taken as anindication of the relative degree of dispersion based on the commonly accepted conception that for the same concentration of solids under similar conditions, the more fluid is the sample, the more completely dispersed are the suspended particles. A Baroid modification of a Stormer viscosimeter was employed in obtaining the data given here.

EXAMPLE III A 50% suspension of pigment-grade titanium dioxide (Titanox-Titanium Pigment Co.) in water was prepared by stirring g. of the pigment in 100 g. of water at high speed for five minutes in a Waring blender. The viscosity of the suspension was measured. Small increments of a 10% aqueous solution of the sodium salt form of the hydrolyzed HCN polymer as prepared in Example I having a specific gravity of 1.065 were then added to the suspension with a one-minute stirring period after each addition. Viscosity measurements were made after each addition of the dispersing agent. The data tabulated below illustrate the remarkable effectiveness of the hydrolyzed hydrocyanic acid polymer as a dispersing agent.

Cone. of Hydrolyzed HCN Polymer (Wt. Percent of Viscosity,

Pigment) cp.

0. Plastic 1 Too thick to measure.

7 EXAMPLE IV f A suspension of S' -Ll of zinc oxide pigment in 54 g.

i of water was prepared by stirring the two together to give a thick pastehaving so-cailed plastic viscosityj Enough i of "a 10% aqueous solution of thesodium' salt form of.

Wthe hydrolyzed polymer of HCN was added topthe suspensionto represent a concentration of 0.39% by weight 1 of the pigrncnt and the mixturewas then stirred thorj oughly. 'I'heviscosityof the suspension was almost irntreated suspension flowed freely upon pouring.

. 1 EXAMPLE V:

The test inEXample IV was'repeated using a suspen "sion of 100 g. of'Kaolin'clay inv 100 g. of water and mediately reduced. to about 10; centipo ses so that the I i .In practice, reduction in viscosity may be achieved by dilution with water, or by the addition. of dispersa'nts, e

The former method, while it maybe satisfactory in specific instances, has many drawbacks and disadvantages and'so the practice of: adding various chemicals. to-drilling'fluids enough of the HCN polymerto represent a concentraj tion 'ofl).53% "by weight or the pigment; Again the 1 thick paste whichoriginallly. had no fluid'properties at all I was converted into a free flowing liqnid'with a viscosity 1 I of approximately 5 centipoises :by the :addition' of; the I 5 In another s ecific embodiment of this invention; 11y

drolyzedpolymers of HCN are 'usedto prepare drilling rnuds having exceptional properties.

":Drilling of an :oil or a 'w'ellb I the 'rietarymethod is performed by rotating a bit attached to the end of a I'mllow drill pipe, known as a drill stem, which extends downward through the well bore. As the drill I 'stem'is rotated from the surface, the bit cuts or grinds away :formation into small fragments known as cuttings which must be removed from the hole in order 'that I the drilling may progress; i 'To' carry away these cuta I tings, a fluid commonly referred to as drilling mud is continuously pum ed down the drill stem; through than- I I nels in the drill bit itself, and then: upward through the Q a nnularspa'ce. between the drill stem and the walls of the borehole to the surface of the earth. In addition to' the primary function of picking up the cuttings pro-- f :dnced'by the drill bit and carrying them to the surface.

the drilling mud serves a number of other purposes. it

must'lubricate and cool the drill stem and bit; it must apply a hydrostatic pressure to the formation to counter balance the pressure of any liquids or gases which may be encountered in the various strata penetrated by the drill bit in order to prevent flow of formation fluid into the borehole; and it must form on the walls of the borehole a thin impervious layer or sheath of solid material which serves to reduce loss of water from the borehole to the formation and provides support for the walls to prevent their collapse into the drilling hole.

The ability of any given mud to carry out these important functions depends upon certain readily measurable physical properties. Viscosity is an important characteristic. The drilling mud must have a viscosity sufficiently high to permit it to effectively suspend and remove the cuttings from the bottom of the well. On the other hand, the viscosity must at the same time be low enough so that the mud may be readily circulated at the desired rates without requiring excessive pump pressures and/ or power consumption.

The properties of the drilling mud are changed during drilling because some of the strata traversed are composed of shales, clays, etc., which become dispersed in the fluid and produce a gradual increase in the viscosity of the drilling mud with continued use. Contamination by salt brincs or as a result of cementing operations likewise causes undesirable increases in viscosity. The custom of using weighting materials, such as barytes or hematite, to increase the density of the mud also results in increased viscosity. If the viscosity is allowed to become too great, difliculties are encountered both in pumping the mud and in removing cuttings from the mud at the surface. Another serious problem with highly viscous fluids is that of gas cutting. The gas from the formato reduce viscosity has become more or less standard. .A large number of chemicals such as pyrophosphates, 'polyphosphates, tannates, =h-umates, and. phytates. have been employed inthe prior art. lnmanycases, howeverp I l the extent to which a drilling fluid can be controlled by such chemicals is limited, I

In accordance with the invention, the viscosity of 11 7 aqueous drilling fluid may becontrolled efiiciently by: in- I 'corporatingi therein: :asufficient: :amount of; hydrolyzed; polymers of HCN. The drilling mud composition ot'the I invention may be describedbriefiy asa mixture, comris I I ing finely divided solid material, an aqueous vehicle in which the solid material is dispersed or suspended, and

agsutficient} amountof hydrolyzed polymers of HCN to maintain the viscosity of: the: fluid at the desired level.

The. finely divided solid material of the invention may, I of course, be any finely'dividedsolid which is capable of being dispersed or suspendedzin an aqueous. liquid vehicle.

Ordinarily; such material will include; hydratable clay or. i 1 i I i 1 colloidalg clay bodies such; as Wyoming bentonite, commercial: medium-yield drilling clays mined in various parts ofthe countryqsuch asinTexas, Tennessee and Louisiana, and those produced whenclaycy subsurface formations arev drilled: E Weighting material added to in I crease specific gravity suchas barytes, iron oxide, calcium 'of mud will produce the desired effect.

, carbonate, silica'and the like may also be included.

The aqueous medium may be fresh water such as is obtained from wells or streams; it may be salt water from the sea or from wells; it may even include oil-in-water emulsions, i. e., water which has become contaminated in some way with small quantities of oil, or to which such oil has been added to gain some desired advantage.

It is contemplated that the drilling muds of the invention may also contain other additives besides the hydrolyzed polymers of HCN of the invention. Materials such as caustic, quebracho, lime, cement, gypsum and the like may be added to the drilling mud at the surface or may be encountered in subsurface formations during drilling operations.

The quantities of the hydrolyzed polymers of HCN to be employed in the drillingmud of the invention will vary with circumstances over a reasonably wide range and the amount employed in a specific suspension or dispersion will depend on these circumstances and the characteristics of the material treated. Ordinarily, satisfactory results will be obtained with quantities ranging from 1 to 4 pounds of the hydrolyzed polymer of HCN per 42-gallon barrel of drilling mud. On the other hand, in some cases where only small improvement in viscosity is desired, as little as 0.5 lb. of the additive per barrel Above 4 lb. per barrel, the small increase in effect in most cases would not warrant the additional cost of the material. The use of'larger amounts of the hydrolyzed polymers of HCN, say in quantities up to 6 lb. per barrel, would not usually have any harmful effect on the mud. Excess ive quantities, however, might lead to over-treatment, i. e., develop an increase in viscosity. The exact amount to be added depends, as previously pointed out, upon the particular mud and on the properties desired. This can be determined, as is the customary procedure for all additives', by simple routine tests at the time the addition is made.

The following examples are presented to illustrate the eifectiveness of the hydrolyzed HCN polymers as viscosity '10 to flow. The measurement of this resistance to flow with the Faun viscosimeter is the yield value which is actually a measurement of the interparticle forces in the mud. Chemical treatment of the mud directly affects the yield maintenance of a constant and preferably a low resistance control agents in drilling muds. value, hence the effectiveness of a particular chemical EXA P VI additive as a thinner or in reducing resistance to flow is Asynthefic drilling mud was prepared containing 35% dlrectly measurable by means of the yield value. Resolids suspended in water. On a dry basis the solids sults of the tests are Presfirfted Table These data consisted of parts by weight of Tennessee Ball clay, 10 o r te hat the addition of themovel polymeric 1 pal-t by weight f bentonite and 4 parts by weight f composltlons of the invention in quantities of from 0.5 lb. Di i Bond clay, M d samples were d up i per barrel and upwards produce a drastic reduction in ing varying quantities of two different samples of hyviscosity of the mud without adversely aifecting itsdrolyzed HCN polymers (designated as polymer No. 1 thixotropic properties or its filtration rate characteristics.

Table I Viscosity Gel Strength Filtration Amt. of Rate, cc. in Additive Additive pH Yield so-Mm.

(lb./bb1.) 600R.P.M. Plastic Point O-Min. lO-Min. API

Faun (cp.) (cp.) (Ila/$00 (g.) (E-) Blank 0 1 5.8 77 124 Polymer No. 1 0. 5 7.2 10 7 6 Do 1.0 2.0 10.5 7 7 1.5 8.5 12.5 s 9 2.0 8.9 14 9 10 3.0 9.3 10.5 10 13 4.0 9.5 16.5 10 13 5.0 9.0 10.5 10 13 0 5.8 12 140 0.5 7.0 11.5 s 7 1.0 7.3 10 7 0 1.5 7.0 10 s 4 2.0 7.8 10 8 4 3.0 3.2 11 7 s 4.0 8.4 12.5 9 7 5.0 3.0 13.5 9 9 and polymer No. 2 in this and the following example) EXAMPLE VII inthe form of their sodium salts. Polymer No. l was the same material used in Examples III, IV, and V and had Frequently viscoslty control agents whlch are Sans a nitrogen content of.14.0%, while polymer No. 2 was factfory muds. zvlth z zg are not from another batch and contained 21% nitrogen. The W en Sa Water use or ma ng e A Samples were then tested by means of standard proce series of tests were run ln sea-water mud, therefore, to dines to evaluate the HCN polymer as a thinner The evaluate the A CN polymers tested 1n Example V in the procedure used was that given in Recommended Prac- Preset":e of dlssolved Salt- The mud Stock p y tice for Standard Field Procedure for Testing Drilling Was T Same as that of p y eXcept thflt'salt Water Fluids of the American Petroleum Institute, third edi- Obialned the Gulf of MeXlCO s d Instead of tio May, 1950, except a otherwise indicated for viscosfresh or dlstllled Water. Results of these tests, presented ity determinations. The flow behavior of the mud was in Table II below, demonstrate that the polymers of the determined with a multispeed Fann V-G viscosimeter. invention are also efiective in this particular mud.

Table II Viscosity Gel Strength Filtration Amt. of Rate, co. in Additive Additive pH Yield BO-Min.

(lb./bbl.) 000 R. P. M. Plastic Point 0Min lOMin. .4191

Faun (on) (cp.) (Hg/ 300 lg.)

0 12.4 P1astic Plastlc Plastic" Plastic. Plastic 60 1.0 11.9 71 14 2.0 11.9 31 .8 3.0 12.0 20 s 4.0 12.0 15.5 s 5.0 12.0 13 7 1.0 12.2 93.5 12 1.5 12.2 10 2.0 12.2 34 10 3.0 12.2 19.5 3 4.0 12.2 15 7 5.0 12.2 12 e A description of this instrument, the plastic flow proper- The remarkable versatility of the HCN polymer as a ties it measures and their significance in drilling mud dispersing agent is well illustrated in Example VIII, control may be found in Melrose and Lilienthal, J. Pet. since it is Well known that many dispersants useful in Tech., T. P. 3061, p. 159 (1951). In general, field conpigment and clay systems, for example, are entirely trol of mud viscosity properties is directed toward the 76 unsatisfactory in soot slurries which are frequently uncommonly difficult to deflocculate.

11 EXAMPLE VIII The efiectiveness of thehydrolyzedHCN polymer for dispersing soot was determined by treating a sample of a soot slurry containing 13.9% soot in water as described in Example III with small increments of a aqueous solution of the polymeric composition. Data obtained are recorded below:

The preceding examples have illustratedtwo specific applications of the hydrolyzedHCN polymers as dispers ants. Aqueous dispersions of other types of finely divided solid materials can be prepared using the HCN polymers. Aqueous dispersions of adhesivesand cement are additional examples of dispersions that can be prepared by incorporating therewith a minor amount of these polymers.

The hydrolyzed HCN polymers described herein are disclosed and claimed in my co-pending application, Serial No. 542,779, filed October 25, 1955.

What is claimed is:

1. A drilling fluid comprising an aqueous suspension of clay containing a hydrolyzed polymer of hydrocyanic acid prepared by polymerizing liquid hydrocyanic acid in the presence of an alkaline catalyst and thereafter hydrolyzing said polymer; by treatment with water in the presence of an alkali, said hydrolyzed polymer being present in an amount sufficient to reduce the viscosity of said driilingfiuidand maintain it in a circulatable state.

2. A drilling fluid comprising an aqueous suspension of clay containing a hydrolyzed polymer of hydrocyanic acid prepared by polymerizing liquid hydrocyanic acid in the presence of an alkaline catalyst and thereafter hydrolyzing said polymer by treatment with Water in the presence of an alkali chosen from the class consisting of the alkali metal hydroxides and ammonium hydroxide, said hydrolyzed polymer being present in an amount suflicient to reduce the viscosity of said drilling fluid and maintain it in a circulatable state.

3. A drilling fluid comprising an aqueous suspension of clay containing a hydrolyzed polymer of hydrocyanic acid prepared by polymerizing substantially anhydrous liquid hydrocyanic acid in the presence of triethyl amine and thereafter hydrolyzing said polymer to its sodium salt form with water and sodium hydroxide, said hydrolyzed polymer being present in an amount sufiicient to reduce the viscosity of said drilling fiuid and maintain it in a circulatable state.

4. An aqueous suspension of a finely divided solid material containing a hydrolyzed polymer of hydrocyanic acid prepared by polymerizing liquid hydrocyanic acid in 1 the, presence. ofan alkaline catalyst and thereafter hydrolyzing said polymer by treatment with water in the presence ofan alkali, said hydrolyzed polymer. being present inan amount in the range from about 0.05% to about 5% by weight of "said finely divided 'solid material.

5. An aqueous suspension ofa finely divided solid material containing a hydrolyzed polymer of hydrocyanic acid prepared by polymerizing liquid hydrocyanic acid in the presence ofan alkaline catalyst and thereafterhydrolyzing said polymer by treatment with water in the presence of an alkali chosen from the class consisting of the alkali metal hydroxides and ammonium hydroxide, said hydrolyzed polymer being present in an amount in the range from abcut 0.05% to about5% by weight of said finely divided solid material.

6. An aqueous suspension of a finely divided solid material containing a hydrolyzed polymer of hydrocyanic acid prepared by polymerizing substantially anhydrous liquid hydrocyanic acid in the presence of triethyl amine and thereafter hydrolyzing said polymer to its sodium salt form with Water and sodium hydroxide, said hydrolyzed polymer being present in an amount in the range from about 0.05% to about 5% by weight of said finely divided solid material.

7. An aqueous suspension of a finely divided pigment containing a hydrolyzed polymer of hydrocyanic acid prepared by polymerizing liquid hydrocyanic acid in the presence of an alkaline catalyst and thereafter hydrolyzing said polymer by treatment with Water in the presence of an alkali, said hydrolyzed polymer being present in an amount in the range from about 0.05% to about 5% by weight of said finely divided pigment.

8. An aqueous suspension of a finely divided pigment containing a hydrolyzed polymer of hydrocyanic acid prepared by polymerizing liquid hydrocyanic acid in the presence of an alkaline catalyst and thereafter hydrolyzing said polymer by treatment with water in the presence of an alkali chosen from the class consisting of the, alkali metal hydroxides-and ammonium hydroxide, said hydrolyzed polymer being present in an amount in the range from about 0.05% to about 5% by Weight of said finely divided pigment.

9. An aqueous suspension of a finely divided pigment containing a hydrolyzed polymer of hydrocyanic acid prepared by polymerizing substantially anhydrous liquid hydrocyanic, acid in the presence of triethyl amine and thereafter hydrolyzing said polymer to its sodium salt form with water and sodium hydroxide, said hydrolyzed polymer being present in an amountin the range from about 0.05 to about 5% by weight of said finely divided pigment.

References Cited in the file of this patent UNITED STATES PATENTS 1,629,161 Herrmann et al. May 17, 1927 2,067,234 Gordan et al Jan. 12, 1937 2,069,543 Adams et a1. Feb. 2, 1937 2,457,591 Moore Dec. 28, 1948 2,552,775 Fischer et a1. May 15, 1951 2,718,497 Oldham et a1. Sept. 20, 1955

Claims (1)

1. A DRILLING FLUID COMPRISING AN AQUEOUS SUSPENSION OF CLAY CONTAINING A HYDROLYZED POLYMER OF HYDROCYANIC ACID PREPARED BY POLYMERIZING LIQUID HYDROCYANIC ACID IN THE PRESENCE OF AN ALKALINE CATALYST AND THEREAFTER HYDROLYZING SAID POLYMER BY TREATMENT WITH WATER IN THE PRESENCE OF AN ALKALI, SAID HYDROLYZED POLYMER BEING PRESENT IN AN AMOUNT SUFFICIENT TO REDUCE THE VISCOSITY OF SAID DRILLING FLUID AND MAINTAIN IT IN A CIRCULATABLE STATE.